| The design and assembly of organic-metal polymers with multi-haptoes ligands and metal salts have attracted much attention due to their novel structures and special applications in many fields.In this paper, five multi-haptoes ligands 1,1'-(1,4-butanediyl)bis-1H-benzimidazole) (L1), 1,1'-(1,4-butanediyl)bis-lH-benzotriazole (L2), 1,1'-(1,3-propylene)-bis-lH-benzotriazole (L3), l,4-bis(triazol-l-ylmethyl)benzene) (L4) and 1,1'-ferrocenedicarboxylic acid (L5) have been synthesized. By the assembling of the above ligands with metal salts, forty-four organic-metal polymers have been obtained at room temperature or under hydrothermal conditions. Furthermore, we investigated the third-order NLO properties, magnetic properties, redox properties, fluorescence properties and thermal properties of the polymers.Firstly, nine novel organic-metal polymers (1 ~ 9) have been synthesized by treatments of 1,1'-(l,4-butanediyl)bis-lH-benzimidazole) with different metal ions. 1 exhibits two-dimensional rhombohedral grid network structure; 2 and 6 are 2-D layered polymer with chair-like units and the cavities of the chair-like units of 2 are occupied by dimers of MeOH; 3 displays 2-D layered structure with less common reversed triangular-prism-shaped units; 4 and 5 show 2-D layered structure with (4,4) grid units; 7 is a 3-D polymer constructed by ligands L1, SO42- and Cd(II) ions. The third-order nonlinear optical (NLO) properties were determined with a 7-ns pulsed laser at 532 run. The results show that these polymers give large third-order NLO absorptive effects and strong refractive behaviors. The hyperpolarizability rvalues are in the range of 6.74 x10-31 ~ 4.31 x10-29 esu, it is comparable to those of the reported clusters and better than organometallic compounds, semiconductors and fullerene. In addition, we found that the third-order NLO properties of organic-metal polymers can be influenced by the ligands, the valence shell structures of metal ions, anions, or structures.Secondly, through the assembly of 1,r-(1,4-butanediyl)bis-lH-benzotriazole and Co(II), Mn(II), Cd(II), Zn(II) or Cu(II), polymers 10 ~ 14 are generated. Similarly, treatments of l,r-(l,3-propylene)-bis-lH-benzotriazole with Ag(I), Ni(II), Co(II) or Zn(II) afford polymers 15 ~ 18. 10 ~ 12 are 2-D rhombohedral grid coordination polymers; 13 possesses a novel concavo-convex chain structure; 14 and 15 are 2-D layered network with hexagonal units; 16 and 17 possess double helix chain structures; 18 exhibits one-dimensional zigzag chain structure. Nearly all polymers display good third-order NLO properties and the optical parameters of 15 are the largest (a2 = 3.2 x 10-8 mW-1, n2 = -2.78x 10-17 m2 W-1,x(3)= 1.29x10-10 esu, r = 2.23 x10-28 esu) among the reported organic-metal polymers.Thirdly, seventeen organic-metal polymers are synthesized by the reacting of l,4-bis(triazol-l-ylmethyl)benzene) with metal salts. Among them, five are Cd(II)-polymers (19 ~ 23), four are Co(H)-polymers (24 ~ 27), three are Mn(II)-polymers (28 ~ 30), the remains are other metal-polymers (31 ~ 35). 21 possesses an infinit 2-D layered structure with distorted tectangular grid units which are different from those of the reported Cd-polymers. 22 displays a three-dimensional framework, which is formed by btx bridging parallel layers. To the author's best knowledge, polymer 22 is the first Cd(II)-polymer in which Cd(II) ion is eight-coordinated in a hexagonal bipyrimidal geometry. In 3-D polymer 23, there are 2-D layers which are formed by bridging NCS' groups and Cd(II) centers. This phenomenon is less common in polymers. 24 is a novel 2-D polymer, in which Co(II) ions are bridged by SO42- and L4. 35 is a 2-D layered polymer with 60-membered metallocyclic ring units consisting of six L1 and six Pb(II) ions. We discussed the influences of temperature, solvents and anions on the composition, structure and the properties of organic-metal polymers. Through the investigation we found that polymers 21, 32, 34 and 35 show good third-order NLO properties.Finally, nine novel organ...
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